Intracluster ion-molecule reactions between V+ and methyl acetate or ethyl acetate clusters

► Intracluster ion-molecule reactions of vanadium ion and alkyl acetate were studied. ► Competitive V+ insertions and fragmentation mechanism were proposed. ► Evidence for H atom migration within heteroclusters is provided by isotope-labeling experiments. ► Density functional theory calculations rationalize the reaction pathways and energetics.